Naphthindazole-4,9-quinones and use thereof for controlling undesirable plant growth

ABSTRACT

Naphthindazole-4,9-quinones of the formula ##STR1## where R 1  to R 5  have the meanings given in the disclosure, and their use for combating unwanted plant growth.

This is a division of application Ser. No. 407,318, filed Sept. 14, 1989, now U.S. Pat. No. 5,007,954.

The present invention relates to naphthindazole-4,9-quinones and use thereof for controlling undesirable plant growth.

It has already been disclosed that indazolequinone derivatives have herbicidal properties (DE-A-2,107,053). Furthermore, naphthindazole-4,9-quinones are known from Chem. Ber. 97 (1964), 2555, and from Liebigs Ann. Chem. (1985), 251, but nothing is said about their use.

We have found that naphthindazole-4,9-quinones of the formula ##STR2## where

R¹ is hydrogen, C₁ -C₁₀ -alkyl, C₂ -C₁₀ -alkenyl, C₂ -C₁₀ -alkynyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl, di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halogen-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl of one or two nitrogen atoms, unsubstituted or halogen-, hydroxyl-, nitro-, amino-, C₁ -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-substituted phenyl or unsubstituted or halogen-substituted benzyl and

R², R³, R⁴ and R⁵ are each independently of the other hydrogen, halogen, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)aminocarbonyl, or unsubstituted or halogen-, trifluoromethyl-, nitro-, cyano-, amino-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio-or C₁ -C₅ -haloalkylthio-substituted phenyl or heteroaryl and in addition

R³ and R⁴ together with the two carbon atoms of the phenyl ring to which they are bonded form a heterocyclic ring or an unsubstituted or halogen-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthio-substituted benzene or naphthalene ring, have good herbicidal properties and are selectively active with respect to crop plants.

In the formula Ia, the radicals R¹, R², R³, R⁴ and R⁵ have the following meanings:

R¹ : hydrogen, C₁ -C₁₀ -alkyl, preferably C₁ -C₄ -alkyl, C₂ -C₁₀ -alkenyl, preferably C₂ -C₄ -alkenyl, C₂ -C₁₀ -alkynyl, preferably C₂ -C₄ -alkynyl, C₁ -C₁₀ -hydroxyalkyl, preferably C₁ -C₄ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, preferably C₂ -C₆ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, preferably C₃ -C₆ -cycloalkyl, C₁ -C₄ -alkylcarbonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylaminocarbonyloxy-C₁ -C₄ -alkyl, unsubstituted or halogen-, C₁ -C₄ -alkyl- or C₁ -C₄ -alkoxy-substituted (in the phenyl) phenylsulfonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl, di(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl of one or two nitrogen atoms, e.g. pyrimidyl, pyridyl or imidazolyl, unsubstituted or halogen-, hydroxyl-, nitro-, amino-, C₁ -C₄ -alkylamino-, di-C₁ -C₄ -alkylamino-, cyano-, C₁ -C₄ -alkyl-, C₁ -C₄ -haloalkyl-, C₁ -C₄ -alkoxy-, C₁ -C₄ -haloalkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₄ -haloalkylthio-monosubstituted or polysubstituted phenyl, unsubstituted or halogen-monosubstituted or -polysubstituted (in the phenyl) benzyl, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert.-amyl, n-hexyl, pentyl-3,1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1,2-dimethyl-4-hexyl, allyl, methallyl, crotyl, 2-ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl, but-1-en-3-yl, 2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloro-sec.-butyl, 2-chloroisobutyl, 2-fluoro-sec.-butyl, 2-fluoroisobutyl, 2-fluoroisopropyl, chloro-tert.-butyl, 2,2,2-trifluoroethyl, hydroxymethyl, 2-hydroxyethyl, 3-hydroxy-n-propyl, 2-hydroxyisopropyl, 2-hydroxy-n-butyl, 3-hydroxy-n-butyl, 4-hydroxy-n-butyl, 2-hydroxyisobutyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxy-n-propyl, 2-methoxyisopropyl, 3-methoxy-n-butyl, 1-methoxy-sec.-butyl, methoxy-tert.-butyl, ethoxy-tert.-butyl, 2-methoxy-n-butyl, 4-methoxy-n-butyl, cyclopropyl, cyclopentyl, cyclohexyl, 2-methylmercaptoethyl, 2-ethylmercaptoethyl, 3-methylmercapto-n-propyl, 3-methylmercapto-n-butyl, 1-methylmercapto-sec.-butyl, methylmercapto-tert.-butyl, 2-methylmercapto-n-butyl, phenyl, 4-chlorophenyl, 3,4-dichlorophenyl, o-, m- or p-tert-butylphenyl, o-, m-or p-methoxyphenyl, o-, m- or p-methylphenyl, 4-methoxy-3-chlorophenyl, 2-methyl-4-chlorophenyl, benzyl, 2,6-dichlorobenzyl, 2-chloro-6-fluorobenzyl, 2,6-difluorobenzyl or o-, m- or p-chlorobenzyl.

R², R³, R⁴, R⁵ : hydrogen, halogen, such as fluorine, chlorine, bromine or iodine, nitro, cyano, hydroxyl, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, preferably C₁ -C₄ -alkyl, C₁ -C₅ -haloalkyl, preferably C₁ -C₃ -haloalkyl, C₁ -C₅ -alkoxy, preferably C₁ -C₃ -alkoxy, C₁ -C₅ -haloalkoxy, preferably C₁ -C₃ -haloalkoxy, C₁ -C₅ -alkylthio, preferably C₁ -C₃ -alkylthio, C₁ -C₅ -haloalkylthio, preferably C₁ -C₃ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, preferably C₂ -C₆ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, preferably C₂ -C₄ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, preferably C₂ -C₄ -alkanoyloxy, C₃ -C₆ -haloalkanoyloxy, preferably C₂ -C₄ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di(C₁ -C₄ -alkyl)-aminocarbonyl, unsubstituted or halogen-, preferably chlorine- or fluorine-, trifluoromethyl-, nitro-, cyano-, amino-, C₁ -C₄ -alkoxy-, C₁ -C₄ -alkylthio- or C₁ -C₅ -haloalkylthio-substituted phenyl or heteroaryl, preferably pyridyl, pyrimidyl, thienyl, furyl or benzimidazolyl, e.g. methylamino, dimethylamino, ethylamino, diethylamino, isopropylamino, diisopropylamino, methylethylamino, n-, iso- or tert.-butylamino, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl, n-pentyl, tert.-amyl, n-hexyl, pentyl-3, 1,2-dimethyl-n-propyl, 1,3-dimethyl-n-butyl, 1-ethyl-2-methyl-n-propyl, 1,2,2-trimethyl-n-propyl, 1,2-dimethyl-n-hexyl, allyl, methallyl, crotyl, 2-ethylhex-2-enyl, hex-5-enyl, 2-methylbut-2-enyl, 2-methylbut-3-enyl, but-1-en-3-yl, 2-methylbut-1-en-4-yl, 2-methylbut-2-en-4-yl, 3-methylbut-1-en-3-yl, propargyl, but-1-yn-3-yl, but-2-ynyl, fluoromethyl, chloromethyl, trifluoromethyl, difluoromethyl, trichloromethyl, dichloromethyl, 2-chloroethyl, 2-chloro-n-propyl, 3-chloro-n-propyl, 2-chloroisopropyl, pentafluoroethyl, 2,2,2-trifluoroethyl, 2-fluoroisopropyl, 3-fluoro-n-propyl, 2-fluoroethyl, methoxy, ethoxy, n- or isopropoxy, n-, iso- or tert.-butoxy, pentoxy, difluoromethoxy, trifluoromethoxy, trichloromethoxy, methylthio, ethylthio, n- or isopropylthio, n-, iso- or tert.-butylthio, difluoromethylthio, trifluoromethylthio, methoxymethyl, ethoxymethyl, 2-methoxyethyl, 3-methoxy-n-propyl, 2-methoxyisopropyl, 2-ethoxyethyl, 3-ethoxy-n-propyl, 2-ethoxyisopropyl, methoxycarbonyl, ethoxycarbonyl, n- or isopropoxycarbonyl, n-, iso-or tert.-butoxycarbonyl, 2-methoxyethoxycarbonyl, ethoxymethoxycarbonyl, 2-ethoxyethoxycarbonyl, phenyl, o-, m- or p-fluorophenyl, o-, m- or p-chlorophenyl, 2,4-difluorophenyl, 2,4-p-trifluoromethylphenyl, 2-, 3- and 4-nitrophenyl, 2-, 3- and 4-cyanophenyl, 2-, 3- and 4-aminophenyl, 2 -, 3- and 4-methoxyphenyl, 2,4-dimethoxyphenyl, 2,4,5-trimethoxyphenyl, 2-, 3- and 4-thiomethylphenyl, heteroaryl such as pyrid-2-yl, pyrid-3-yl, pyrid-4-yl, thien-2-yl, thien-3-yl, fur-2-yl, fur-3-yl, benzimidazol-2-yl, 3-chloropyrid-6-yl, 2-methylfur-5-yl, 2-methylthien-5-yl and 4,6-dimethylpyrimid-2-yl, acetyl, propionyl, butyryl, isobutyryl, valeroyl, isovaleroyl, pivaloyl, chloroacetyl, dichloroacetyl, trichloroacetyl, fluoroacetyl, difluoroacetyl, trifluoroacetyl, 3,3,3-trifluoropropionyl, pentafluoropropionyl, 2-chloropropionyl, 2,2-dichloropropionyl, 2-fluoropropionyl or 2,2-difluoropropionyl.

R³ and R⁴ may also form together with the two carbon atoms of the phenyl ring to which they are bonded an unsubstituted or fluorine-, chlorine-, bromine-, nitro-, cyano-, amino-, hydroxyl-, trifluoromethyl-, C₁ -C₅ -alkyl-, preferably C₁ -C₃ -alkyl-, C₁ -C₅ -alkoxy-, C₁ -C₅ -haloalkylthio-, C₁ -C₅ -haloalkoxy- or C₁ -C₅ -alkylthio-, preferably C₁ -C₃ -alkylthio-, substituted benzene or naphthalene ring.

Examples of heterocyclic rings formed by R³ and R⁴ together with the two carbon atoms of the phenyl ring to which they are bonded are 1,4-dioxane, 1,3-dioxolane, pyrazole, indole, thiophene, triazole and piperazine. Examples of the corresponding substituted rings are 2,2-dimethyl-1,3-dioxalane, 1-methylpyrazole, 1-methylindole, N,N'-dimethylpiperazine, 2,2-diphenyl-1,3-dioxolane, and 2-oxo-1,3-dioxolane.

Naphthindazole-4,9-quinones of the formula Ia where R¹ is C₁ -C₄ -alkyl or C₂ -C₄ -alkenyl are preferred. Preference is further given to those compounds of the formula Ia where the substituents R² to R⁵ are each independently of the others hydrogen, hydroxyl, halogen, nitro, cyano, amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino. Preference is given in particular to compounds where R² to R⁵ are each hydrogen, hydroxyl or halogen.

The naphthindazole-4,9-quinones of the formula ##STR3## where

R¹, R², R³, R⁴ and R⁵ are each as defined for the formula Ia, with the proviso that R¹ is not hydrogen or methyl, are novel.

The naphthindazole-4,9-quinones of the formula I are obtained by reacting the 5-arylmethylpyrazol-4-yl carbonyl halides of the formula ##STR4## where R¹, R², R³, R⁴ and R⁵ are each as defined above and Hal is halogen, in an inert solubilizer in the presence of a Friedel-Crafts catalyst, and converting the resulting compounds of the formula ##STR5## where R¹, R², R³, R⁴ and R⁵ are each as defined above, in the presence of a diluent with oxidizing agents into the naphthindazole-4,9-quinones of the formula I.

Suitable inert solubilizers for this purpose are carbon disulfide, nitromethane, nitrobenzene, 1,2-dichloroethane, 1,1,2,2-tetrachloroethane, sulfolane, trichloroethylene and 1,1,1-trichloroethane.

Suitable Friedel-Crafts catalysts are aluminum trichloride, boron trifluoride, tin tetrachloride, titanium tetrachloride, zinc chloride, boron trichloride, trifluoroacetic acid, sulfuric acid, aluminum bromide, gallium chloride, iron(III) chloride, antimony pentachloride, antimony trichloride and zirconium tetrachloride. The amount of catalyst is from 5 to 500, preferably from 100 to 250, mol %, based on starting acid chloride of the formula II.

The reaction advantageously takes place at from 0° to 150° C.

The oxidation of compounds III is advantageously carried out in an inert diluent, such as acetic acid or alcoholic or alkali metal hydroxide solution, in the presence or absence of water, at from 0° to 120° C. Suitable oxidizing agents are hydrogen peroxide and chromium(IV) oxide.

The oxidation is advantageously carried out by dissolving the starting compounds III in dilute, aqueous-alcoholic solutions of alkali metal hydroxides at temperatures of from 0° C. to 120° C., preferably from 50° C. to 100° C., and adding excess aqueous hydrogen peroxide solution. The reaction will in general have ended after 4-8, but not more than 24, hours. The solid end product is filtered off with suction and may be recrystallized or chromatographed for purification.

The synthesis of the 5-arylmethylpyrazol-4-yl carbonyl halides II can be effected in a conventional manner in accordance with the following scheme: ##STR6##

The naphthindazole-4,9-quinones of the formula I are likewise obtained on reacting substituted 1,4-naphthoquinones of the formula ##STR7## where R², R³, R⁴ and R⁵ are each as defined above, with diazomethane in the presence of inert diluents, for example aliphatic or alicyclic ethers, oxidizing the resulting compounds of the formula ##STR8## where R², R³, R⁴ and R⁵ are each as defined above, in an inert diluent and alkylating the resulting naphthindazole-4,9-quinones of the formula ##STR9## where R², R³, R⁴ and R⁵ are each as defined above, with an alkylating agent of the formula

    R.sup.1 --X                                                (VII)

where

R¹ is as defined above and

X is p-toluenesulfonate, mesylate, brosylate, halogen or a group of the formula ##STR10## where R¹ is as defined above, in a diluent in the presence of a base at from -30° C. to +100° C.

The reaction of the 1,4-naphthoquinones IV with diazomethane can be carried out in a conventional manner (Houben-Weyl, Methoden der org. Chemie, volume 7/3a, page 553 (1977)). The oxidation of compounds V is possible inter alia with hydrogen peroxide, chromium(VI) oxide or atmospheric oxygen in an inert diluent, such as dilute acetic acid or methyl t-butyl ether.

The alkylation of the naphthindazole-4,9-quinones VI with the alkylating agent VII takes place in a conventional manner in a diluent, for example water or acetone or mixtures thereof, in the presence of a base, such as alkali metal or alkaline earth metal hydroxides, alkali metal or alkaline earth metal carbonates or alkali metal or alkaline earth metal bicarbonates. It is preferable to work at from 10° to 30° C.

All the other starting compounds and reaction products whose preparation has not been described in detail are either known or can be prepared by known principles.

PREPARATION EXAMPLES EXAMPLE 1 ##STR11##

A suspension of 20.6 g (0.13 mol) of 1,4-naphthoquinone in 500 ml of methyl t-butyl ether is admixed under a protective gas atmosphere at 0° C. with 400 ml of a 3.5×10⁻⁴ M solution (0.14 mol) of diazomethane in diethyl ether. After the addition has ended, the suspension is heated to room temperature, and air is passed through the reaction mixture overnight. The precipitate formed is then filtered off with suction, washed with 100 ml of methyl t-butyl ether and stirred into 75 ml of hot ethanol. It is filtered off with suction, washed with 100 ml of ethanol and dried.

Yield: 12.1 g (47% of theory).

Melting point: 180° C. decomposition.

EXAMPLE 2 ##STR12##

6.0 g (0.03 mol) of naphthindazole-4,9-quinone (Example 1) are suspended in 100 ml of 80% strength aqueous acetone and admixed at room temperature in succession with 3.2 g (0.03 mol) of sodium carbonate and 7.3 g (0.06 mol) of 1-bromo-2-propene. The mixture is stirred overnight and then refluxed for three hours. It is cooled down, admixed with a further 1.1 g (0.01 mol) of sodium carbonate and 2.4 g (0.02 mol) of 1-bromo-2-propene and refluxed for a further two hours. It is then concentrated under reduced pressure and extracted four times with 100 ml of dichloromethane each time. The combined extracts are dried over sodium sulfate and concentrated. The crystalline residue is chromatographed over silica gel (mobile phase: cyclohexane/ethyl acetate) to obtain 4.6 g (64% of theory) of 1-(propen-2-yl)naphthindazole-4,9-quinone of melting point 105°-108° C.

EXAMPLE 3 ##STR13##

a) 1.25 g (0.005 mol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-yl carboxylic acid (preparation: G. Menozzi, L. Mosti and P. Schenone, J. Heterocycl. Chem. 24 (1987), 1669) are dissolved in 2 ml of thionyl chloride and refluxed for one hour. Excess thionyl chloride is then removed under reduced pressure (12 mmHg), the residue is taken up in 20 ml of diethyl ether, and the mixture is stirred with 2.0 g of active charcoal. The mixture is filtered after 30 minutes, the filtrate is concentrated under reduced pressure to give 1.25 g (93% of theory) of acid chloride as a colorless oil.

b) 1.25 g (4.6 mmol) of 5-(4-chlorophenylmethyl)-1-methylpyrazol-4-yl carbonyl chloride are dissolved in 5 ml of nitromethane and added to a 0° C. solution of 1.85 g (14 mmol) of aluminum chloride in 20 ml of nitromethane. The mixture is stirred at room temperature overnight and then poured into a mixture of 50 g of ice and 20 ml of concentrated hydrochloric acid. The organic phase is separated off, the aqueous phase is extracted twice more with 50 ml of dichloromethane each time and the combined extracts are dried over sodium sulfate. Removing the solvent under reduced pressure leaves 1.10 g (100% of theory) of 6-chloro-9-hydro-1-methylnaphthindazol-4-one of melting point>270° C.

¹ H-NMR (250 MHz, DMSO-d₆): 4.05 (s; 3H), 4.45 (s; 2H), 7.35 (dd, J=9.2 and 0.2 Hz; 1H), 7.90 (d, J=9.0 Hz; 1H), 8.20 (d, J=0.2 Hz; 1H), 8.45 (s; 1H).

c) 1.10 g (4.6 mmol) of 6-chloro-9-hydro-1-methylnaphthindazol-4-one are dissolved in a mixture of 10 ml of 10% strength sodium hydroxide solution and 50 ml of methanol by heating (80° C.). The solution is cooled down to 60° C., and 5 ml of a 30% strength solution of hydrogen peroxide are added. The mixture is stirred at room temperature overnight, and the precipitated quinone is then filtered off with suction, giving 0.85 g (57% of theory) of 1-methyl-6-chloronaphthindazol-4,9-quinone of melting point 219° C.

¹ H-NMR (250 MHz, CDCl₃): 4.35 (s; 3H), 7.72 (d, J=9.0 Hz; 1H), 8.05 (s; 1H), 8.18 (s; 1H), 8.18 (d, J=9.0 Hz; 1H).

The following compounds of the formulae I and Ia can be obtained in a similar manner:

    __________________________________________________________________________     Example no.                                                                           R.sup.1            R.sup.2 -R.sup.5                                                                              Melting point [°C.]            __________________________________________________________________________     4      CH.sub.3           H              181                                   5      CH.sub.2 CH.sub.3  H              151-152                               6      isopropyl          H              126                                   7      n-propyl           H                                                    8      n-butyl            H               69                                   9      t-butyl            H              152                                   10     2-pentyl           H              164                                   11     cyclopentyl        H                                                    12     cyclohexyl         H              148                                   13     CH.sub.2CF.sub.3   H              171                                   14     CH.sub.2OH         H                                                    15     CH.sub.2CH.sub.2OH H              158                                   16                                                                                     ##STR14##         H              109                                   17                                                                                     ##STR15##         H              116                                   18                                                                                     ##STR16##         H              179                                   19                                                                                     ##STR17##         H              155                                   20     CH.sub.2COOC.sub.2 H.sub.5                                                                        H              149                                   21     CH.sub.2COOH       H                                                    22                                                                                     ##STR18##         H                                                    23                                                                                     ##STR19##         H                                                    24                                                                                     ##STR20##         H                                                    25     CH.sub.2 CH.sub.2SCH.sub.3                                                                        H                                                    26     CH.sub.2SCH.sub.3  H                                                    27     CH.sub.2CCH        H              193                                   28     CH.sub.2CCBr       H                                                    29     phenyl             H              221                                   30     benzyl             H              154                                   31     2-(4,6-dimethylpyrimidinyl)                                                                       H              237                                   32     2-pyridinyl        H              221                                   33     2-(2-imidazoline)  H                                                    34     2,4-dichlorophenyl H                                                    35     2,4,6-trichlorophenyl                                                                             H                                                    36     4-fluorophenyl     H                                                    37     2,4-difluorophenyl H                                                    38     2,4,6-trifluorophenyl                                                                             H                                                    39     4-methoxyphenyl    H                                                    40     2,4-dimethoxyphenyl                                                                               H                                                    41     4-thiomethylphenyl H                                                    42     4-trifluoromethylphenyl                                                                           H                                                    __________________________________________________________________________     Example no.                                                                           R.sup.1 R.sup.2 R.sup.3                                                                             R.sup.4                                                                             R.sup.5 Melting point [°C.]            __________________________________________________________________________     43     CH.sub.3                                                                               F       H    H    H       195                                   44     CH.sub.3                                                                               H       F    H    H                                             45     CH.sub.3                                                                               H       H    F    H       173                                   46     CH.sub.3                                                                               H       H    H    F                                             47     CH.sub.3                                                                               Cl      H    H    H                                             48     CH.sub.3                                                                               H       Cl   H    H       219                                   49     CH.sub.3                                                                               H       H    Cl   H       226                                   50     CH.sub.3                                                                               H       H    H    Cl                                            51     CH.sub.3                                                                               Br      H    H    H                                             52     CH.sub.3                                                                               H       H    H    Br      190-192                               53     CH.sub.3                                                                               Cl      H    H    Cl                                            54     CH.sub.3                                                                               H       Cl   H    Cl      230                                   55     CH.sub.3                                                                               H       Cl   Cl   H                                             56     CH.sub.3                                                                               F       H    H    F                                             57     CH.sub.3                                                                               H       F    H    F                                             58     CH.sub.3                                                                               H       F    F    H                                             59     CH.sub.3                                                                               OH      H    H    H       190                                   60     CH.sub.3                                                                               H       OH   H    H                                             61     CH.sub.3                                                                               H       H    OH   H                                             62     CH.sub.3                                                                               H       H    H    OH      212                                   63     CH.sub.3                                                                               OH      H    H    OH      224-227                               64     CH.sub.3                                                                               OCH.sub.3                                                                              H    H    H                                             65     CH.sub.3                                                                               H       OCH.sub.3                                                                           H    H       193                                   66     CH.sub.3                                                                               H       H    OCH.sub.3                                                                           H       173                                   67     CH.sub.3                                                                               H       H    H    OCH.sub.3                                                                              230                                   68     CH.sub.3                                                                               OCH.sub.3                                                                              H    CH.sub.3                                                                            H       212-213                               69     CH.sub.3                                                                               OH      H    H    OCH.sub.3                                     70     CH.sub.3                                                                               OCH.sub.3                                                                              H    H    OH                                            71     CH.sub.3                                                                               OCH.sub.3                                                                              OCH.sub.3                                                                           H    OCH.sub.3                                     72     CH.sub.3                                                                               OH      OCH.sub.3                                                                           H    OCH.sub.3                                     73     CH.sub.3                                                                               OCH.sub.3                                                                              H    OCH.sub.3                                                                           H       212                                   74     CH.sub.3                                                                               OCH.sub.3                                                                              H    OCH.sub.3                                                                           OH                                            75     CH.sub.3                                                                               OH      H    OCH.sub.3                                                                           H       208                                   76     CH.sub.3                                                                               H       OCH.sub.3                                                                           H    OCH.sub.3                                     77     CH.sub.3                                                                               H       OCH.sub.3                                                                           H    OH                                            78     CH.sub.3                                                                               H       OCH.sub.2CH.sub.2 O                                                                      H                                             79     CH.sub.3                                                                               H       OCH.sub.2O                                                                               H       252                                   80     CH.sub.3                                                                               H       OH   OH   H                                             81     CH.sub.3                                                                               SCH.sub.3                                                                              H    H    H                                             82     CH.sub.3                                                                               H       SCH.sub.3                                                                           H    H                                             83     CH.sub.3                                                                               H       H    SCH.sub.3                                                                           H                                             84     CH.sub.3                                                                               H       H    H    SCH.sub.3                                     85     CH.sub.3                                                                                ##STR21##                                                                             H    H    H       220                                   86     CH.sub.3                                                                               H       H    H                                                                                    ##STR22##                                    87     CH.sub.3                                                                               CH.sub.3                                                                               H    H    H                                             88     CH.sub.3                                                                               H       CH.sub.3                                                                            H    H       177                                   89     CH.sub.3                                                                               H       H    CH.sub.3                                                                            H       136                                   90     CH.sub.3                                                                               H       H    H    CH.sub.3                                                                               218                                   91     CH.sub.3                                                                               CH.sub.3                                                                               H    H    CH.sub.3                                                                               143                                   92     CH.sub.3                                                                               CF.sub.3                                                                               H    H    H                                             93     CH.sub. 3                                                                              H       CF.sub.3                                                                            H    H                                             94     CH.sub.3                                                                               H       H    CF.sub.3                                                                            H                                             95     CH.sub.3                                                                               H       H    H    CF.sub.3                                      96     CH.sub.3                                                                               H       CH.sub.3                                                                            H    OH      154                                   97     CH.sub.3                                                                               OH      H    CH.sub.3                                                                            H       175                                   98     CH.sub.3                                                                               H       C.sub.4 H.sub.4                                                                          OH      288                                   99     CH.sub.3                                                                               H       C.sub.4 H.sub.4                                                                          H                                             100    CH.sub.3                                                                               OH      C.sub.4 H.sub.4                                                                          H                                             101    CH.sub.3                                                                               H       C.sub.4 H.sub.4                                                                           ##STR23##                                                                             253                                   102    CH.sub.3                                                                                ##STR24##                                                                             C.sub.4 H.sub.4                                                                          H       231                                   103    CH.sub.3                                                                               F       C.sub.4 H.sub.4                                                                          OH                                            104    CH.sub.3                                                                               NO.sub.2                                                                               H    H    H                                             105    CH.sub.3                                                                               H       H    H    NO.sub.2                                      106    CH.sub.3                                                                               NH.sub.2                                                                               H    H    H                                             107    CH.sub.3                                                                               H       H    H    NH.sub.2                                      108    CH.sub.3                                                                                ##STR25##                                                                             H    H    H                                             109    CH.sub.3                                                                               H       H    H                                                                                    ##STR26##                                    110    CH.sub.3                                                                               CN      H    H    H                                             111    CH.sub.3                                                                               H       CN   H                                                  112    CH.sub.3                                                                               H       H    H    CN                                            113    CH.sub.3                                                                               C.sub.6 H.sub.5                                                                        H    H    H                                             114    CH.sub.3                                                                               H       C.sub.6 H.sub.5                                                                     H    H       185                                   115    CH.sub.3                                                                               H       H    C.sub.6 H.sub.5                                                                     H                                             116    CH.sub.3                                                                               H       H    H    C.sub.6 H.sub.5                               117    CH.sub.3                                                                               COOCH.sub.3                                                                            H    H    H                                             118    CH.sub.3                                                                               H       H    H    COOCH.sub.3                                   119    CH.sub.3                                                                               COOH    H    H    H                                             120    CH.sub.3                                                                               H       H    H    COOH                                          121    CH.sub.3                                                                               CONHCH.sub.3                                                                           H    H    H                                             122    CH.sub.3                                                                               H       H    H    CONHCH.sub.3                                  123    CH.sub.3                                                                               CON(CH.sub.3).sub.2                                                                    H    H    H                                             124    CH.sub.3                                                                               H       H    H    CON(CH.sub.3).sub.2                           125    C.sub.6 H.sub.5                                                                        OH      H    H    OH      208                                   126    C.sub.6 H.sub.5                                                                        OH      H    H    H                                             127    C.sub.6 H.sub.5                                                                        H       H    H    OH                                            128    C.sub.6 H.sub.5                                                                        F       H    H    H                                             129    C.sub.6 H.sub.5                                                                        H       H    F    H                                             130    C.sub.6 H.sub.5                                                                        H       H    H    F                                             131    C.sub.6 H.sub.5                                                                        Cl      H    H    H                                             132    C.sub.6 H.sub.5                                                                        H       H    H    Cl                                            133    C.sub.6 H.sub.5                                                                        OH      H    OCH.sub.3                                                                           H                                             134    C.sub.6 H.sub.5                                                                        OCH.sub.3                                                                              H    OH   H                                             135    C.sub.6 H.sub.5                                                                        H       OCH.sub.3                                                                           H    OH                                            136    C.sub.6 H.sub.5                                                                        CF.sub.3                                                                               H    H    H                                             137    C.sub.6 H.sub.5                                                                        H       H    CF.sub.3                                                                            H                                             138    C.sub.6 H.sub.5                                                                        H       H    H    CF.sub.3                                      139    C.sub.6 H.sub.5                                                                        NH.sub.2                                                                               H    H    H                                             140    C.sub.6 H.sub.5                                                                        H       H    NH.sub.2                                                                            H                                             141    C.sub.6 H.sub.5                                                                        H       H    H    NH.sub.2                                      142    C.sub.6 H.sub.5                                                                        H       NO.sub.2                                                                            H    H                                             143    C.sub.6 H.sub.5                                                                        NO.sub.2                                                                               H    H    H                                             144    C.sub.6 H.sub.5                                                                        F       F    H    H                                             145    isopropyl                                                                              H       CF.sub.3                                                                            H    H                                             146    isopropyl                                                                              H       H    CF.sub.3                                                                            H                                             147    isopropyl                                                                              H       H    H    CF.sub.3                                      148    isopropyl                                                                              H       CH.sub.3                                                                            H    OH                                            149    isopropyl                                                                              OH      H    CH.sub.3                                                                            H                                             150    isopropyl                                                                              H       C.sub.4 H.sub.4                                                                          OH                                            151    isopropyl                                                                              H       C.sub.4 H.sub.4                                                                          H                                             152    isopropyl                                                                              OH      C.sub.4 H.sub.4                                                                          H                                             153    isopropyl                                                                              H       C.sub.4 H.sub.4                                                                           ##STR27##                                    154    isopropyl                                                                               ##STR28##                                                                             C.sub.4 H.sub.4                                                                          H                                             155    isopropyl                                                                              F       C.sub.4 H.sub.4                                                                          OH                                            156    isopropyl                                                                              NO.sub.2                                                                               H    H    H                                             157    isopropyl                                                                              H       H    H    NO.sub.2                                      158    isopropyl                                                                              NH.sub.2                                                                               H    H    H                                             159    isopropyl                                                                              H       H    H    NH.sub.2                                      160    isopropyl                                                                               ##STR29##                                                                             H    H    H                                             161    isopropyl                                                                              H       H    H    NHCOCH.sub.3                                  162    isopropyl                                                                              CN      H    H    H                                             163    isopropyl                                                                              H       CN   H    H                                             164    isopropyl                                                                              H       H    H    CN                                            165    isopropyl                                                                              C.sub.6 H.sub.5                                                                        H    H    H                                             166    isopropyl                                                                              H       C.sub.6 H.sub.5                                                                     H    H                                             167    isopropyl                                                                              H       H    C.sub.6 H.sub.5                                                                     H                                             168    isopropyl                                                                              H       H    H    C.sub.6 H.sub.5                               169    isopropyl                                                                              COOCH.sub.3                                                                            H    H    H                                             170    isopropyl                                                                              H       H    H    COOCH.sub.3                                   171    isopropyl                                                                              F       H    H    H                                             172    isopropyl                                                                              H       F    H    H                                             173    isopropyl                                                                              H       H    F    H                                             174    isopropyl                                                                              H       H    H    F                                             175    isopropyl                                                                              Cl      H    H    H                                             176    isopropyl                                                                              H       Cl   H    H                                             177    isopropyl                                                                              H       H    Cl   H                                             178    isopropyl                                                                              H       H    H    Cl                                            179    isopropyl                                                                              Br      H    H    H                                             180    isopropyl                                                                              F       H    H    Br                                            181    isopropyl                                                                              Cl      H    H    Cl                                            182    isopropyl                                                                              H       Cl   H    Cl                                            183    isopropyl                                                                              H       Cl   Cl   H                                             184    isopropyl                                                                              F       H    H    F                                             185    isopropyl                                                                              H       F    H    F                                             186    isopropyl                                                                              H       F    F    H                                             187    isopropyl                                                                              OH      H    H    H                                             188    isopropyl                                                                              H       OH   H    H                                             189    isopropyl                                                                              H       H    OH   H                                             190    isopropyl                                                                              H       H    H    OH                                            191    isopropyl                                                                              OH      H    H    OH                                            192    isopropyl                                                                              OCH.sub.3                                                                              H    H    H                                             193    isopropyl                                                                              H       OCH.sub.3                                                                           H    H       176                                   194    isopropyl                                                                              H       H    OCH.sub.3                                                                           H       160                                   195    isopropyl                                                                              H       H    H    OCH.sub.3                                     196    isopropyl                                                                              OCH.sub.3                                                                              H    H    OCH.sub.3                                     197    isopropyl                                                                              OH      H    H    OCH.sub.3                                     198    isopropyl                                                                              OCH.sub.3                                                                              H    H    OH                                            199    isopropyl                                                                              OCH.sub.3                                                                              OCH.sub.3                                                                           H    OCH.sub.3                                     200    isopropyl                                                                              OH      OCH.sub.3                                                                           H    OCH.sub.3                                     201    isopropyl                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                           OCH.sub.3                                     202    isopropyl                                                                              OCH.sub.3                                                                              H    OCH.sub.3                                                                           OH                                            203    isopropyl                                                                              OH      H    OCH.sub.3                                                                           H                                             204    isopropyl                                                                              H       OCH.sub.3                                                                           H    OCH.sub.3                                     205    isopropyl                                                                              H       OCH.sub.3                                                                           H    OH                                            206    isopropyl                                                                              H       OCH.sub.2CH.sub.2 O                                                                      H                                             207    isopropyl                                                                              H       O CH.sub.2O                                                                              H                                             208    isopropyl                                                                              H       OH   OH   H                                             209    isopropyl                                                                              SCH.sub.3                                                                              H    H    H                                             210    isopropyl                                                                              H       SCH.sub.3                                                                           H    H                                             211    isopropyl                                                                              H       H    SCH.sub.3                                                                           H                                             212    isopropyl                                                                              H       H    H    SCH.sub.3                                     213    isopropyl                                                                               ##STR30##                                                                             H    H    H                                             214    isopropyl                                                                              H       H    H                                                                                    ##STR31##                                    215    isopropyl                                                                              CH.sub.3                                                                               H    H    H                                             216    isopropyl                                                                              H       CH.sub.3                                                                            H    H                                             217    isopropyl                                                                              H       H    CH.sub.3                                                                            H                                             218    isopropyl                                                                              H       H    H    CH.sub.3                                      219    isopropyl                                                                              CH.sub.3                                                                               H    H    CH.sub.3                                      220    isopropyl                                                                              CF.sub.3                                                                               H    H    H                                             221    isopropyl                                                                              COOH    H    H    H                                             222    isopropyl                                                                              H       H    H    COOH                                          223    isopropyl                                                                              CONHCH.sub.3                                                                           H    H    H                                             224    isopropyl                                                                              H       H    H    CONHCH.sub.3                                  225    isopropyl                                                                              CON(CH.sub.3).sub.2                                                                    H    H    H                                             226    isopropyl                                                                              H       H    H    CON(CH.sub.3).sub.2                           227    CH.sub.2CCH                                                                            OH      H    H    H                                             228    CH.sub.2CCH                                                                            H       H    H    OH                                            229    CH.sub.2CCH                                                                            OCH.sub.3                                                                              H    H    H                                             230    CH.sub.2CCH                                                                            H       H    H    OCH.sub.3                                     231    CH.sub.2CCH                                                                            OH      H    OCH.sub.3                                                                           H                                             232    CH.sub.2CCH                                                                            H       OCH.sub.3                                                                           H    OH                                            233    CH.sub.2CCH                                                                            F       H    H    H                                             234    CH.sub.2CCH                                                                            H       H    F    H                                             235    CH.sub.2CCH                                                                            H       H    H    F                                             236    CH.sub.2CCH                                                                            Cl      H    H    H                                             237    CH.sub.2CCH                                                                            H       H    H    Cl                                            238    CH.sub.2CCH                                                                            H       H    H    Br                                            239    CH.sub.2CCH                                                                            CF.sub.3                                                                               H    H    H                                             240    CH.sub.2CCH                                                                            H       H    CF.sub.3                                                                            H                                             241    CH.sub.2CCH                                                                            H       H    H    CF.sub.3                                      242    CH.sub.2CCH                                                                            H       OCH.sub.3                                                                           H    H                                             243    CH.sub.2CCH                                                                            H       H    OCH.sub.3                                                                           H                                             244    CH.sub.2CCH                                                                            CN      H    H    H                                             245    CH.sub.2CCH                                                                            H       H    CN   H                                             246    CH.sub.2CCH                                                                            H       H    H    CN                                            247    allyl   F       H    H    H                                             248    allyl   H       F    H    H                                             249    allyl   H       H    F    H                                             250    allyl   H       H    H    F                                             251    allyl   Cl      H    H    H                                             252    allyl   H       Cl   H    H                                             253    allyl   H       H    Cl   H                                             254    allyl   H       H    H    Cl                                            255    allyl   Br      H    H    H                                             256    allyl   H       H    H    Br                                            257    allyl   Cl      H    H    Cl                                            258    allyl   H       Cl   H    Cl                                            259    allyl   H       Cl   Cl   H                                             260    allyl   F       H    H    F                                             261    allyl   H       F    H    F                                             262    allyl   H       F    F    H                                             263    allyl   OH      H    H    H                                             264    allyl   H       OH   H    H                                             265    allyl   H       H    OH   H                                             266    allyl   H       H    H    OH                                            267    allyl   OH      H    H    OH                                            268    allyl   OCH.sub.3                                                                              H    H    H                                             269    allyl   H       OCH.sub.3                                                                           H    H                                             270    allyl   H       H    OCH.sub.3                                                                           H                                             271    allyl   H       H    H    H                                             272    allyl   OCH.sub.3                                                                              H    H    OCH.sub.3                                     273    allyl   OH      H    H    OCH.sub.3                                     274    allyl   OCH.sub.3                                                                              H    H    OH                                            275    allyl   OCH.sub.3                                                                              OCH.sub.3                                                                           H    OCH.sub.3                                     276    allyl   OH      OCH.sub.3                                                                           H    OCH.sub.3                                     277    allyl   OCH.sub.3                                                                              H    OCH.sub.3                                                                           OCH.sub.3                                     278    allyl   OCH.sub.3                                                                              H    OCH.sub.3                                                                           OH                                            279    allyl   OH      H    OCH.sub.3                                                                           H                                             280    allyl   H       OCH.sub.3                                                                           H    OCH.sub.3                                     281    allyl   H       OCH.sub.3                                                                           H    OH                                            282    allyl   H       OCH.sub.2CH.sub.2 O                                                                      H                                             283    allyl   H       OCH.sub.2O                                                                               H                                             284    allyl   H       OH   OH   H                                             285    allyl   SCH.sub.3                                                                              H    H    H                                             286    allyl   H       SCH.sub.3                                                                           H    H                                             287    allyl   H       H    SCH.sub.3                                                                           H                                             288    allyl   H       H    H    SCH.sub.3                                     289    allyl                                                                                   ##STR32##                                                                             H    H    H                                             290    allyl   H       H    H                                                                                    ##STR33##                                    291    allyl   CH.sub.3                                                                               H    H    H                                             292    allyl   H       CH.sub.3                                                                            H    H                                             293    allyl   H       H    CH.sub.3                                                                            H                                             294    allyl   H       H    H    H                                             295    allyl   CH.sub.3                                                                               H    H    CH.sub.3                                      296    allyl   CF.sub.3                                                                               H    H    H                                             297    allyl   H       CF.sub.3                                                                            H    H                                             298    allyl   H       H    CF.sub.3                                                                            H                                             299    allyl   H       H    H    CF.sub.3                                      300    allyl   H       CH.sub.3                                                                            H    OH                                            301    allyl   OH      H    CH.sub.3                                                                            H                                             302    allyl   H       C.sub.4 H.sub.4                                                                          OH                                            303    allyl   H       C.sub.4 H.sub.4                                                                          H                                             304    allyl   OH      C.sub.4 H.sub.4                                                                          H                                             305    allyl   H       C.sub.4 H.sub.4                                                                           ##STR34##                                    306    allyl                                                                                   ##STR35##                                                                             C.sub.4 H.sub.4                                                                          H                                             307    allyl   F       C.sub.4 H.sub.4                                                                          OH                                            308    allyl   NO.sub.2                                                                               H    H    H                                             309    allyl   H       H    H    NO.sub.2                                      310    allyl   NH.sub.2                                                                               H    H    H                                             311    allyl   H       H    H    NH.sub.2                                      312    allyl                                                                                   ##STR36##                                                                             H    H    H                                             313    allyl   H       H    H                                                                                    ##STR37##                                    314    allyl   CN      H    H    H                                             315    allyl   H       CN   H    H                                             316    allyl   H       H    H    CN                                            317    allyl   C.sub.6 H.sub.5                                                                        H    H    H                                             318    allyl   H       C.sub.6 H.sub.5                                                                     H    H                                             319    allyl   H       H    C.sub.6 H.sub.5                                                                     H                                             320    allyl   H       H    H    C.sub.6 H.sub.5                               321    allyl   COOCH.sub.3                                                                            H    H    H                                             322    allyl   H       H    H    COOCH.sub.3                                   323    allyl   COOH    H    H    H                                             324    allyl   H       H    H    COOH                                          325    allyl   CONHCH.sub.3                                                                           H    H    H                                             326    allyl   H       H    H    CONHCH.sub.3                                  327    allyl   CON(CH.sub.3).sub.2                                                                    H    H    H                                             328    allyl   H       H    H    CON(CH.sub.3).sub.2                           329    allyl   N(CH.sub.3).sub.2                                                                      H    H    H                                             330    allyl   H       H    H    N(CH.sub. 3).sub.2                            331    allyl   F       H    H    NH.sub.2                                      332    allyl   NH.sub.2                                                                               H    H    F                                             __________________________________________________________________________

The active ingredients have a herbicidal action and are selective in crop plants.

The compounds, and herbicidal agents containing them, may be applied for instance in the form of directly sprayable solutions, powders, suspensions (including high-percentage aqueous, oily or other suspensions), dispersions, emulsions, oil dispersions, pastes, dusts, broadcasting agents, or granules by spraying, atomizing, dusting, broadcasting or watering. The forms of application depend entirely on the purpose for which the agents are being used, but they must ensure as fine a distribution of the active ingredients according to the invention as possible.

For the preparation of solutions, emulsions, pastes and oil dispersions to be sprayed direct, mineral oil fractions of medium to high boiling point, such as kerosene or diesel oil, further coal-tar oils, and oils of vegetable or animal origin, aliphatic, cyclic and aromatic hydrocarbons such as benzene, toluene, xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes and their derivatives such as methanol, ethanol, propanol, butanol, cyclohexanol, cyclohexanone, chlorobenzene, isophorone, etc., and strongly polar solvents such as N,N-dimethylformamide, dimethyl sulfoxide, N-methylpyrrolidone, water, etc. are suitable.

Aqueous formulations may be prepared from emulsion concentrates, pastes, oil dispersions or wettable powders by adding water. To prepare emulsions, pastes and oil dispersions the ingredients as such or dissolved in an oil or solvent may be homogenized in water by means of wetting or dispersing agents, adherents or emulsifiers. Concentrates which are suitable for dilution with water may be prepared from active ingredient, wetting agent, adherent, emulsifying or dispersing agent and possibly solvent or oil.

Examples of surfactants are: alkali metal, alkaline earth metal and ammonium salts of aromatic sulfonic acids, e.g., ligninsulfonic acid, phenolsulfonic acid, naphthalenesulfonic acid and dibutylnaphthalenesulfonic acid, and of fatty acids, alkyl and alkylaryl sulfonates, and alkyl, lauryl ether and fatty alcohol sulfates, alkali metal and alkaline earth metal salts of dibutylnaphthalenesulfonic acid, lauryl ether sulfate, fatty alcohol sulfates, and salts of sulfated hexadecanols, heptadecanols, and octadecanols, salts of fatty alcohol glycol ethers, condensation products of sulfonated naphthalene and naphthalene derivatives with formaldehyde, condensation products of naphthalene or naphthalenesulfonic acids with phenol and formaldehyde, polyoxyethylene octylphenol ethers, ethoxylated isooctylphenol, ethoxylated octylphenol and ethoxylated nonylphenol, alkylphenol polyglycol ethers, tributylphenyl polyglycol ethers, alkylaryl polyether alcohols, isotridecyl alcohol, fatty alcohol ethylene oxide condensates, ethoxylated castor oil, polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, lauryl alcohol polyglycol ether acetal, sorbitol esters, lignin-sulfite waste liquors and methyl cellulose.

Powders, dusts and broadcasting agents may be prepared by mixing or grinding the active ingredients with a solid carrier.

Granules, e.g., coated, impregnated or homogeneous granules, may be prepared by bonding the active ingredients to solid carriers. Examples of solid carriers are mineral earths such as silicic acid, silica gels, silicates, talc, kaolin, attapulgus clay, limestone, lime, chalk, bole, loess, clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate, magnesium oxide, ground plastics, fertilizers such as ammonium sulfate, ammonium phosphate, ammonium nitrate, and ureas, and vegetable products such as grain meals, bark meal, wood meal, and nutshell meal, cellulosic powders, etc.

The formulations contain from 0.1 to 95, and preferably 0.5 to 90, % by weight of active ingredient.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 2 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 4 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, and 5 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

III. 20 parts by weight of compound no. 6 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and finely distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

IV. 20 parts by weight of compound no. 59 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanone, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into 100,000 parts by weight of water and uniformly distributing it therein, an aqueous dispersion is obtained containing 0.02% by weight of the active ingredient.

V. 20 parts by weight of compound no. 45 is well mixed with 3 parts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 17 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 60 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in 20,000 parts by weight of water, a spray liquor is obtained containing 0.1% by weight of the active ingredient.

VI. 3 parts by weight of compound no. 4 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 6 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 20 parts by weight of compound no. 59 is intimately mixed with 2 parts of the calcium salt of dodecylbenzenesulfonic acid, 8 parts of a fatty alcohol polyglycol ether, 2 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts of a paraffinic mineral oil. A stable oily dispersion is obtained.

The active ingredients or the herbicidal agents containing them may be applied pre- or postemergence. If certain crop plants tolerate the active ingredients less well, application techniques may be used in which the herbicidal agents are sprayed from suitable equipment in such a manner that the leaves of sensitive crop plants are if possible not touched, and the agents reach the soil or the unwanted plants growing beneath the crop plants (post-directed, lay-by treatment).

The application rates depend on the objective to be achieved, the time of the year, the plants to be combated and their growth stage, and are from 0.01 to 5.0, preferably 0.05 to 3.0, kg of active ingredient per hectare.

The herbicidal action of the naphthindazoles of the formula I on the growth of test plants is illustrated by the following greenhouse experiments.

The vessels employed were plastic flowerpots having a volume of 300 cm³ and filled with a sandy loam containing about 3.0% humus. The seeds of the test plants were sown separately, according to species.

For the postemergence treatment, the plants were grown, depending on growth form, to a height of 3 to 15 cm before being treated. In this treatment method, either plants which had been sown in the pots and grown there were selected, or they were cultivated separately as seedlings and transplanted to the pots a few days before being treated with the compounds suspended or emulsified in water. The application rates for postemergence treatment were 0.5 and 1.0 kg/ha.

The pots were set up in the greenhouse, species from warmer climates in warmer areas (20° to 35° C.) and species from moderate climates at 10° to 20° C. The experiments were run for from 2 to 4 weeks. During this time the plants were tended and their reactions to the various treatments assessed.

The assessment scale was 0 to 100, 100 denoting nonemergence or complete destruction of at least the visible plant parts, and 0 denoting no damage or normal growth.

The plants used in the greenhouse experiments were Amaranthus retroflexus, Ipomoea spp., Setaria italica, Solanum nigrum and Veronica spp.

The compounds of Examples 2, 4, 6, 45 and 59, applied postemergence at rates of 0.5 and 1.0 kg/ha, combated unwanted plants excellently.

In view of the number of application methods possible, the compounds according to the invention, or agents containing them, may be used in a further large number of crops for removing unwanted plants. The following crops are given by way of example:

    ______________________________________                                         Botanical name          Common name                                            ______________________________________                                         Allium cepa             onions                                                 Ananas comosus          pineapples                                             Arachis hypogaea        peanuts                                                                        (groundnuts)                                           Asparagus officinalis   asparagus                                              Avena sativa            oats                                                   Beta vulgaris spp. altissima                                                                           sugarbeets                                             Beta vulgaris spp. rapa fodder beets                                           Beta vulgaris spp. esculenta                                                                           table beets,                                                                   red beets                                              Brassica napus var. napus                                                                              rapeseed                                               Brassica napus var. napobrassica                                                                       swedes                                                 Brassica napus var. rapa                                                                               turnips                                                Brassica rapa var. silvestris                                                  Camellia sinensis       tea plants                                             Carthamus tinctorius    safflower                                              Carya illinoinensis     pecan trees                                            Citrus limon            lemons                                                 Citrus maxima           grapefruits                                            Citrus reticulata       mandarins                                              Citrus sinensis         orange trees                                           Coffea arabica (Coffea canephora,                                                                      coffee plants                                          Coffea liberica)                                                               Cucumis melo            melons                                                 Cucumis sativus         cucumbers                                              Cynodon dactylon        Bermudagrass                                           Daucus carota           carrots                                                Elais guineensis        oil palms                                              Fragaria vesca          strawberries                                           Glycine max             soybeans                                               Gossypium hirsutum (Gossypium arboreum,                                                                cotton                                                 Gossypium herbaceum, Gossypium vitifolium)                                     Helianthus annuus       sunflowers                                             Helianthus tuberosus    Jerusalem                                                                      artichoke                                              Hevea brasiliensis      rubber plants                                          Hordeum vulgare         barley                                                 Humulus lupulus         hops                                                   Ipomoea batatas         sweet potatoes                                         Juglans regia           walnut trees                                           Lactuca sativa          lettuce                                                Lens culinaris          lentils                                                Linum usitatissimum     flax                                                   Lycopersicon lycopersicum                                                                              tomatoes                                               Malus spp.              apple trees                                            Manihot esculenta       cassava                                                Medicago sativa         alfalfa (lucerne)                                      Mentha piperita         peppermint                                             Musa spp.               banana plants                                          Nicotiana tabacum (N. rustica)                                                                         tobacco                                                Olea europaea           olive trees                                            Oryza sativa            rice                                                   Panicum miliaceum       millet                                                 Phaseolus lunatus       limabeans                                              Phaseolus mungo         mungbeans                                              Phaseolus vulgaris      snapbeans,                                                                     green beams,                                                                   dry beans                                              Pennisetum glaucum      pearl millet                                           Petroselinum crispum spp. tuberosum                                                                    parsley                                                Picea abies             Norway spruce                                          Abies alba              fir trees                                              Pinus spp.              pine trees                                             Pisum sativum           English peas                                           Prunus avium            cherry trees                                           Prunus domestica        plum trees                                             Prunus dulcis           almond trees                                           Prunus persica          peach trees                                            Pyrus communis          pear trees                                             Ribes sylvestre         redcurrants                                            Ribes uva-crispa        gooseberries                                           Ricinus communis        castor-oil plants                                      Saccharum officinarum   sugar cane                                             Secale cereale          rye                                                    Sesamum indicum         sesame                                                 Solanum tuberosum       Irish potatoes                                         Sorghum bicolor (s. vulgare)                                                                           sorghum                                                Sorghum dochna          sorgo                                                  Spinacia oleracea       spinach                                                Theobroma cacao         cacao plants                                           Trifolium pratense      red clover                                             Triticum aestivum       wheat                                                  Triticum durum          durum wheat                                            Vaccinium corymbosum    blueberries                                            Vaccinium vitis-idaea   cranberries                                            Vicia faba              tick beans                                             Vigna sinensis (V. unguiculara)                                                                        cow peas                                               Vitis vinifera          grapes                                                 Zea mays                Indian corn,                                                                   sweet corn, maize                                      ______________________________________                                    

To increase the spectrum of action and to achieve synergistic effects, the naphthindazoles of the formula I may be mixed and applied together with numerous representatives of other herbicidal or growth-regulating active ingredient groups. Examples of suitable components are diazines, 4H-3,1-benzoxazine derivatives, benzothiadiazinones, 2,6-dinitroanilines, N-phenylcarbamates, thiolcarbamates, halocarboxylic acids, triazines, amides, ureas, diphenyl ethers, triazinones, uracils, benzofuran derivatives, cyclohexane-1,3-dione derivatives, quinolinecarboxylic acids, (het)aryloxyphenoxypropionic acids and salts, esters and amides thereof, etc.

It may also be useful to apply the novel compounds of the formula I, either alone or in combination with other herbicides, in admixture with other crop protection agents, e.g., agents for combating pests or phytopathogenic fungi or bacteria. The compounds may also be mixed with solutions of mineral salts used to remedy nutritional or trace element deficiencies. Non-phytotoxic oils and oil concentrates may also be added. 

We claim:
 1. A herbicidal composition containing inert additives and a herbicidally effective amount of a naphthindazole-4,9-quinone of the formula ##STR38## where: R¹ is C₂ -C₁₀ -alkyl, C₂ -C₁₀ -alkenyl, C₂ -C₁₀ -alkynyl, C₁ -C₁₀ -haloalkyl, C₁ -C₁₀ -hydroxyalkyl, C₂ -C₁₄ -alkoxyalkyl, C₂ -C₁₄ -alkylthioalkyl, C₃ -C₇ -cycloalkyl, C₁ -C₄ -alkylcabonyloxy-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyloxy-C₁ -C₄ -alkyl, phenylaminocarbonyloxy-C₁ -C₄ -alkyl which is unsubstituted or substituted in the phenyl moiety by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, phenylsulfonyloxy-C₁ -C₄ -alkyl which is unsubstituted or substituted in the phenyl moiety by halogen, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy, C₁ -C₄ -alkoxycarbonyl-C₁ -C₄ -alkyl, hydroxycarbonyl-C₁ -C₄ -alkyl, aminocarbonyl-C₁ -C₄ -alkyl, C₁ -C₄ -alkylaminocarbonyl-C₁ -C₄ -alkyl, di-(C₁ -C₄ -alkyl)aminocarbonyl-C₁ -C₄ -alkyl, halo-C₃ -C₄ -alkynyl, unsubstituted or halogen- or C₁ -C₄ -alkyl-substituted heteroaryl radical with one or two nitrogen atoms, phenyl which is unsubstituted or substituted by halogen, hydroxy, nitro, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, cyano, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, C₁ -C₄ -haloalkoxy, C₁ -C₄ -haloalkyl, C₁ -C₄ -alkylthio or C₁ -C₄ -haloalkylthio, or unsubstituted or halogen-substituted benzyl, andR², R³, R⁴ and R⁵ are identical or different and each denotes hydrogen, halogen, nitro, cyano, hydroxy, amino, C₁ -C₄ -alkylamino, di-C₁ -C₄ -alkylamino, C₁ -C₆ -alkyl, C₁ -C₅ -haloalkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkoxy, C₁ -C₅ -alkylthio, C₁ -C₅ -haloalkylthio, C₂ -C₁₀ -alkoxyalkyl, carboxyl, C₂ -C₆ -alkoxycarbonyl, C₂ -C₆ -alkanoyloxy, C₂ -C₆ -haloalkanoyloxy, C₁ -C₄ -alkylcarbonylamino, C₁ -C₄ -alkylaminocarbonyl, di-(C₁ -C₄ -alkyl)-aminocarbonyl, or phenyl or heteroaryl, each of which is unsubstituted or substituted by halogen, trifluoromethyl, nitro, cyano, amino, C₁ -C₄ -alkoxy, C₁ -C₄ -alkylthio or C₁ -C₅ -haloalkylthio, and R³ and R⁴, together with the two carbon atoms of the phenyl ring to which they are attached, form a heterocyclic ring or a benzene or naphthalene ring which is unsubstituted or substituted by halogen, nitro, cyano, amino, hydroxy, trifluoromethyl, C₁ -C₅ -alkyl, C₁ -C₅ -alkoxy, C₁ -C₅ -haloalkylthio, C₁ -C₅ -haloalkoxy or C₁ -C₅ -alkylthio.
 2. The herbicidal composition of claim 1, wherein R¹ of the naphthindazole-4,9-quinone is C₂ -C₄ -alkyl or C₂ -C₄ -alkenyl.
 3. The herbicidal composition of claim 1, wherein R² to R⁵ of the naphthindazole-4,9-quinone are identical or different and are each hydrogen, hydroxy, halogen, nitro, cyano, amino, C₁ -C₄ -alkylamino or di-C₁ -C₄ -alkylamino.
 4. The herbicidal composition of claim 1, wherein R¹ of the naphthindazole-4,9-quinone is 2-propenyl and R², R³, R⁴ and R⁵ are each hydrogen.
 5. The herbicidal composition of claim 1, wherein R¹ of the naphthindazole-4,9-quinone is 1-methylethyl and wherein R², R³, R⁴ and R⁵ are each hydrogen. 